Diphosphines bonds

Tetraphosphabicyclo[1.1.0]butane 58 (Scheme 24) has been reported [60, 61]. The SE is much higher than cyclotriphosphane 14 or P (see Sect. 3.3.4), but stiU lower than bicyclo[1.1.0]butane 45 [62, 63], in agreement with the lone pair effect (see Sect. 2.1.4). Interestingly, the bridgehead bonds have been observed to be shorter than a normal P-P bond (2.218 A in diphosphine) [64]. The related... 

The crystal structures of a number of diphosphine disulphides (121) and (122) show a remarkable constancy in the bond lengths. Two types of molecule are observed in the crystal of the tetramethyl compound (121, X = Y = Me). The crystal structure of triphenylphosphine oxide (P—C 176 pm, P—O 164 pm) varies little from that observed in the uranium oxide complexes, and does not confirm P—O bond lengthening in complexes, as indicated by vp=.o (see Section 3C). 

The strong backbonding from the chelated diphosphine Pd(0) metal center to the electron-poor exocylic C=C bond of the QM moieties results in remarkable stability of the complex, with the QM ligand remaining unaffected in water or alcohol, even upon heating. 

Dinuclear complexes with bridging phosphido, hydrido, and diphosphine ligands were formed via some interesting transformations, such as P—C bond formation, P—H bond activation, and conversion of a chelate diphosphine to one bridging two metal centers.259... 

The characterization and crystal structure of the dimer [Pt2( -dppm)3] (dppm = bis(diphenyl-phosphino)methane), first reported as a deep red complex in 1978, was described by Manojlovic-Muir et al. in 1986.11 The structure, the first of its type, is made up of two parallel and almost eclipsed trigonal-planar platinum moieties bridged by three diphosphine ligands. The Pf Pt separation is 3.0225(3) A, too long to be considered a bond.11 [Pt2(//-dppm)3] catalyzes the hydrogenation/reduction of carbon dioxide with dimethylamine to give dimethylformamide12 (Equation (1)) and the reverse reaction.13... 

Independently, triangulo-Hg3 compounds with stabilizing chelating diphosphine and diarsine ligands have been prepared, 82-387 crystal-structure analyses have been solved (the Hg—Hg bonds, 280 pm, are longer than before), and careful multinuclear NMR spectra measured and analysed. 

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